CA2608183A1 - Process for preparation of alkyl and alcoxyalkyl-.alpha.-cyanoacrylates by depolymerisation of poly(alkyl-.alpha.-cyanoacrylates) or poly(alcoxyalkyl-.alpha.-cranoacrylates) and its usage as technical and/or medical adhesive - Google Patents
Process for preparation of alkyl and alcoxyalkyl-.alpha.-cyanoacrylates by depolymerisation of poly(alkyl-.alpha.-cyanoacrylates) or poly(alcoxyalkyl-.alpha.-cranoacrylates) and its usage as technical and/or medical adhesive Download PDFInfo
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- CA2608183A1 CA2608183A1 CA002608183A CA2608183A CA2608183A1 CA 2608183 A1 CA2608183 A1 CA 2608183A1 CA 002608183 A CA002608183 A CA 002608183A CA 2608183 A CA2608183 A CA 2608183A CA 2608183 A1 CA2608183 A1 CA 2608183A1
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- Prior art keywords
- alpha
- alkyl
- cyanoacrylates
- poly
- cyanoacrylate
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- 229920001651 Cyanoacrylate Polymers 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000853 adhesive Substances 0.000 title claims abstract description 12
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 5
- -1 ethyl- Chemical group 0.000 claims description 9
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 16
- 238000009833 condensation Methods 0.000 abstract description 7
- 230000005494 condensation Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 7
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 abstract description 2
- 239000007859 condensation product Substances 0.000 abstract description 2
- 239000007792 gaseous phase Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 231100001261 hazardous Toxicity 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 241001417511 Ardis Species 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000003014 phosphoric acid esters Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- UMCLCZMPTREESK-UHFFFAOYSA-N 2-ethoxyethyl 2-cyanoacetate Chemical compound CCOCCOC(=O)CC#N UMCLCZMPTREESK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241000282342 Martes americana Species 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical class CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004830 Super Glue Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- DJACTCNGCHPGOI-UHFFFAOYSA-N butyl 2-cyanoacetate Chemical compound CCCCOC(=O)CC#N DJACTCNGCHPGOI-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Abstract
This invention is related to the preparation of alkyl or alcoxyalkyl-.alpha.-cyanoacrylates in monomeric form by depolymerisation of the corresponding poly(alkyl-.alpha.-cyanoacrylates) or poly(alcoxyalkyl-.alpha.-cyanoacrylates) (PCA). The PCA's are obtained preferably by base-catalyzed condensation of a cyanoacetate with formaldehyde (or a polymer of the latter). According to the invention, the poly(alkyl-.alpha.-cyanoacrylate) or poly(alcoxyalky-.alpha.-cyanoacrylate), the condensation product, is mixed with a depolymerisation system comprising phosphorus pentoxide P2O5, hydroquinone, ortho-phosphoric acid and para-toluenesulfonic acid. This process is realized in a batch reactor fitted with a condenser, heated at a temperature in the range of 100-300~C, under a vacuum of 0.5-50 Torr (7.10-5 - 7.10-3 MPa) and gives rise to monomeric alkyl-.alpha.-cyanoacrylates or monomeric alcoxyalkyl-.alpha.-cyanoacrylates, being stable in both gaseous and liquid phase. After an additional purification by vacuum distillation, these cyanoacrylates can be used as fast setting technical or medical adhesives.
Description
Description PROCESS FOR PREPARATION OF ALKYL AND AL-COXYALKYL-a-CYANOACRYLATES BY DEPOLY-MERISATION OF POLY(ALKYL-a CYANOACRYLATES) OR
POLY(ALCOXYALKYL-a-CYANOACRYLATES) AND ITS
USAGE AS TECHNICAL AND/OR MEDICAL ADHESIVE
Field of the invention [ 1] This invention relates to the preparation of a-cyanoacrylates in monomeric form and is particularly concerned with the depolymerisation of poly(alkyl-a-cyanoacrylates) or poly(alcoxyalkyl-a-cyanoacrylates) (PCA) to produce monomers applicable in technical or medical adhesives. More specifically, the invention discloses an improved method for controlled depolymerisation of polymeric cyanoacrylates in the presence of a depolymerisation system containing specified amounts of phosphorous pentoxide (P205), hydroquinone, ortho-phosphoric acid and para-toluenesulfonic acid. The depolymerisation method disclosed allows the attainment of high-yield and high-purity alkyl or alcoxyalkyl-a-cyanoacrylates in reactors of simple design, with a minimum quantity of liquid waste and without the use of hazardous gases.
Background of the invention [2] Cyanoacrylate monomers, when applied as a thin layer between two surfaces made out of similar or different materials, e.g. metals, polymers (with the exception of polyolefins), wood, stone, living tissue, etc. are able to bond to them rapidly and without the use of heat or catalysts. Conventionally, the esters of the a-cyanoacrylates are prepared using a two-stage reaction. In the first stage, the corresponding cyanoacetate is made to react with formaldehyde (as gas, aqueous solution or in polymeric form) in a basic environment to form poly(alkyl-a-cyanoacrylates).
In the second stage, the polymer is cracked (i.e., depolymerised), purified and stabilized to obtain the cyanoacrylate adhesive.
POLY(ALCOXYALKYL-a-CYANOACRYLATES) AND ITS
USAGE AS TECHNICAL AND/OR MEDICAL ADHESIVE
Field of the invention [ 1] This invention relates to the preparation of a-cyanoacrylates in monomeric form and is particularly concerned with the depolymerisation of poly(alkyl-a-cyanoacrylates) or poly(alcoxyalkyl-a-cyanoacrylates) (PCA) to produce monomers applicable in technical or medical adhesives. More specifically, the invention discloses an improved method for controlled depolymerisation of polymeric cyanoacrylates in the presence of a depolymerisation system containing specified amounts of phosphorous pentoxide (P205), hydroquinone, ortho-phosphoric acid and para-toluenesulfonic acid. The depolymerisation method disclosed allows the attainment of high-yield and high-purity alkyl or alcoxyalkyl-a-cyanoacrylates in reactors of simple design, with a minimum quantity of liquid waste and without the use of hazardous gases.
Background of the invention [2] Cyanoacrylate monomers, when applied as a thin layer between two surfaces made out of similar or different materials, e.g. metals, polymers (with the exception of polyolefins), wood, stone, living tissue, etc. are able to bond to them rapidly and without the use of heat or catalysts. Conventionally, the esters of the a-cyanoacrylates are prepared using a two-stage reaction. In the first stage, the corresponding cyanoacetate is made to react with formaldehyde (as gas, aqueous solution or in polymeric form) in a basic environment to form poly(alkyl-a-cyanoacrylates).
In the second stage, the polymer is cracked (i.e., depolymerised), purified and stabilized to obtain the cyanoacrylate adhesive.
[3] The above reaction scheme was proposed for the first time by Ardis in U.S.
Pat. No 2,467,927, which discloses the condensation of formalin (ca. 40 wt. % of formaldehyde in water) with alkyl cyanoacetate using basic catalysts. The polymer thus formed is depolymerised in the presence of catalytic amounts of P 05, employing a gaseous inhibitor of the back polymerization - sulphur dioxide SO2 or nitric oxide NO. Later US patent No 2,721,858 by Joyner and Hawkins discloses the substitution of formalin, in the stage of condensation, with a formaldehyde polymer and the combined use of phosphorus pentoxide and hydroquinone in the stage of depolymerisation.
Stable monomers were only obtained when SO z -gas was passed through the reactor during the depolymerisation stage.
Pat. No 2,467,927, which discloses the condensation of formalin (ca. 40 wt. % of formaldehyde in water) with alkyl cyanoacetate using basic catalysts. The polymer thus formed is depolymerised in the presence of catalytic amounts of P 05, employing a gaseous inhibitor of the back polymerization - sulphur dioxide SO2 or nitric oxide NO. Later US patent No 2,721,858 by Joyner and Hawkins discloses the substitution of formalin, in the stage of condensation, with a formaldehyde polymer and the combined use of phosphorus pentoxide and hydroquinone in the stage of depolymerisation.
Stable monomers were only obtained when SO z -gas was passed through the reactor during the depolymerisation stage.
[4] US patent No 2,756,251 by Joyner and Shearer describes a similar depoly-merisation system comprising phosphorous pentoxide and hydroquinone (polymerization inhibitors for the liquid cyanoacrylate). The SOZ gas is equally used to inhibit the spontaneous polymerization of the cyanoacrylate vapours. The use of high-boiling tertiary phosphoric acid esters as reaction media for depolymerisation, e.g., tricresyl phosphate, was here proposed for the first time. These phosphate esters should have boiling temperatures about 60-80 C higher than the depolymerisation temperature. The amount of tricresyl phosphate required in the process disclosed in this patent is about 0.9 times that of the polymeric raw material, thus creating significant amounts of liquid waste. The reaction is conducted as a batch process.
[5] An analogous method for making alkyl-a-cyanoacrylates was proposed by Robert Rabinowitz in US patent No 3,444,233 disclosing continuous depolymerisation of poly(alkyl-a-cyanoacrylate) esters. The polymer is first admixed with an inert liquid of high boiling point, such as tricresyl phosphate adding one or more polymerization inhibitors, such as phosphorus pentoxide and hydroquinone. This mixture is then de-polymerised by heating a thin layer of this mixture in vacuum to produce high-purity monomeric a-cyanoacrylate vapours. The continuous process disclosed in this patent requires the use of large amounts of tricresyl phosphate (1.45 times the amount of the polycyanoacrylic acid esters), thus resulting in serious liquid pollution and disposal problems. Again, to get stable monomeric alkyl cyanoacrylates useful as instant adhesives, the depolymerisation has to be carried out in a stream of the hazardous and corrosive SOZ gas.
[6] US patent 5,436,363 by Wang et al. discloses a continuous process for making cyanoacrylates, which utilizes a thin-layer evaporator and a two-condenser heat transfer system. A poly(alkyl-a-cyanoacrylate) feed containing catalytic amounts of P
z 05 and hydroquinone without a high-boiling medium is introduced into a thin-film evaporator so as to carry out the depolymerisation reaction. The monomeric vapours produced by this process, where no high-boiling medium is used, do not require sta-bilization by SO z-gas. They are then subjected to a two-stage heat transfer process for condensation and purification. The first stage involves a high temperature condenser operating at ca. 150 C that collects a fraction containing primarily 'dimers' of cyanoacrylate (i.e., dicyanoglytarates). Subsequently, the gaseous phase enters a low-temperature condenser, operating at -8 C, where the cyanoacrylate monomer is collected. The advantages of this scheme employing thin layer evaporator and an in-termediate condenser are: (i) the elimination of the need of using a high-boiling heat transfer medium; (ii) the elimination of the use of hazardous gases (SO z or NO); (iii) the attainment of a high-yield and high-purity final product of cyanoacrylate mo nomers. The major disadvantages of the proposed process are related to: (i) a quite complex reactor design; (ii) the need for a continuous, large-scale production, which is not always appropriate when smaller volumes of monomeric cyanoacrylates are needed, as in the case of medical adhesives.
z 05 and hydroquinone without a high-boiling medium is introduced into a thin-film evaporator so as to carry out the depolymerisation reaction. The monomeric vapours produced by this process, where no high-boiling medium is used, do not require sta-bilization by SO z-gas. They are then subjected to a two-stage heat transfer process for condensation and purification. The first stage involves a high temperature condenser operating at ca. 150 C that collects a fraction containing primarily 'dimers' of cyanoacrylate (i.e., dicyanoglytarates). Subsequently, the gaseous phase enters a low-temperature condenser, operating at -8 C, where the cyanoacrylate monomer is collected. The advantages of this scheme employing thin layer evaporator and an in-termediate condenser are: (i) the elimination of the need of using a high-boiling heat transfer medium; (ii) the elimination of the use of hazardous gases (SO z or NO); (iii) the attainment of a high-yield and high-purity final product of cyanoacrylate mo nomers. The major disadvantages of the proposed process are related to: (i) a quite complex reactor design; (ii) the need for a continuous, large-scale production, which is not always appropriate when smaller volumes of monomeric cyanoacrylates are needed, as in the case of medical adhesives.
[7] Other reaction schemes, not including condensation or depolymerisation processes, are also worth mentioning:
1. the protection of the cyanoacrylate monomer in the condensation stage, by formation of its anthracene Diels-Alder adduct, with subsequent cyanoacrylate liberation, involving the reaction of the adduct with maleic anhydride, avoiding the stage of depolymerisation and originating stable alkyl-cyanoacrylates, useful as industrial adhesives, as exemplified by U.S.
Patents No. 3,463,804 by Ray and Doran and 4,012,402 (Buck);
2. the transesterification of the cyanoacrylate monomers with alcohols, as described in USSR authorship certification No 726086 by Y. B. Vojtekunas et al.;
3. the direct esterification of cyanoacrylic acid with alcohols is reported in German patent 3,415,181 by Schulter and Marten;
4. the thermal decomposition of alkyl 2-cyano-3-alkoxypropionates and the 3-acyloxy analogues are described in U.S. Patent No 2,467,926 by Ardis;
5. the pyrolysis of the cyanohydrin acetates of pyruvic acid esters is described in U.S. Pat. No 2,391,251 by Long.
1. the protection of the cyanoacrylate monomer in the condensation stage, by formation of its anthracene Diels-Alder adduct, with subsequent cyanoacrylate liberation, involving the reaction of the adduct with maleic anhydride, avoiding the stage of depolymerisation and originating stable alkyl-cyanoacrylates, useful as industrial adhesives, as exemplified by U.S.
Patents No. 3,463,804 by Ray and Doran and 4,012,402 (Buck);
2. the transesterification of the cyanoacrylate monomers with alcohols, as described in USSR authorship certification No 726086 by Y. B. Vojtekunas et al.;
3. the direct esterification of cyanoacrylic acid with alcohols is reported in German patent 3,415,181 by Schulter and Marten;
4. the thermal decomposition of alkyl 2-cyano-3-alkoxypropionates and the 3-acyloxy analogues are described in U.S. Patent No 2,467,926 by Ardis;
5. the pyrolysis of the cyanohydrin acetates of pyruvic acid esters is described in U.S. Pat. No 2,391,251 by Long.
[8] The major disadvantages of all these processes are their high complexity, requiring the isolation and the purification of many intermediates and their very long duration (typically 10-16 h per batch), which renders them unsuitable for industrial applications.
Especially inappropriate for the synthesis of medical adhesives is the use of Diels-Alder protection that requires the implementation of readily sublimating carcinogenic compounds with condensed benzene rings that can migrate into the final adhesive and enter in contact with living tissue.
Summary of the invention [9] The present invention discloses a versatile process for the production of alkyl and alkoxyalkyl-a-cyanoacrylates, applicable on technical and medical adhesives, by in-troducing a new stabilization system at the stage of depolymerisation. The general formula of these compounds is the following:
C- N
H2C=C
c =a a -R
General formula of the alkyl or alkoxyalkyl-a-cyanoacrylates R = alkyl C i-C
16 or alkoxyalkyl residue.
Especially inappropriate for the synthesis of medical adhesives is the use of Diels-Alder protection that requires the implementation of readily sublimating carcinogenic compounds with condensed benzene rings that can migrate into the final adhesive and enter in contact with living tissue.
Summary of the invention [9] The present invention discloses a versatile process for the production of alkyl and alkoxyalkyl-a-cyanoacrylates, applicable on technical and medical adhesives, by in-troducing a new stabilization system at the stage of depolymerisation. The general formula of these compounds is the following:
C- N
H2C=C
c =a a -R
General formula of the alkyl or alkoxyalkyl-a-cyanoacrylates R = alkyl C i-C
16 or alkoxyalkyl residue.
[10] The new process proposed is simple in terms of reactor design, does not involve the generation of much liquid waste and excludes the use of hazardous inhibition gases.
Detailed description of the invention [11] The new process disclosed in the present patent makes use of the aforementioned condensation-depolymerisation scheme, employing a new stabilization system in the stage of depolymerisation, which comprises phosphorus pentoxide, hydroquinone, ortho-phosphoric acid and para-toluenesulfonic acid, in specific concentrations, as indicated hereafter. The co-inventors have identified the strong stabilization effect of the said four-component system, eliminating significantly the undesired back poly-merization of the monomeric cyanoacrylates (in both liquid and gaseous state) in the depolymerisation stage. Thus, the polymer phase remains less viscous and better de-polymerisable during the entire depolymerisation, without the necessity of use of high-boiling solvents. Furthermore, the cyanoacrylate vapours do not polymerize spon-taneously, avoiding the use of gaseous polymerization inhibitors, such as SO z . It is an advantage of the process proposed that it allows the use of a one-condenser batch reactor of a versatile and simple design, useful for the small- and medium-scale production of more sophisticated cyanoacrylate monomers applied as medical adhesives. Another advantage of the process proposed is the fact that it does not require the use of non-recyclable, high-boiling point solvents (such as tricresyl phosphate) and/or dangerous, corrosive gases (SO2) which required special safety and purification procedures.
Detailed description of the invention [11] The new process disclosed in the present patent makes use of the aforementioned condensation-depolymerisation scheme, employing a new stabilization system in the stage of depolymerisation, which comprises phosphorus pentoxide, hydroquinone, ortho-phosphoric acid and para-toluenesulfonic acid, in specific concentrations, as indicated hereafter. The co-inventors have identified the strong stabilization effect of the said four-component system, eliminating significantly the undesired back poly-merization of the monomeric cyanoacrylates (in both liquid and gaseous state) in the depolymerisation stage. Thus, the polymer phase remains less viscous and better de-polymerisable during the entire depolymerisation, without the necessity of use of high-boiling solvents. Furthermore, the cyanoacrylate vapours do not polymerize spon-taneously, avoiding the use of gaseous polymerization inhibitors, such as SO z . It is an advantage of the process proposed that it allows the use of a one-condenser batch reactor of a versatile and simple design, useful for the small- and medium-scale production of more sophisticated cyanoacrylate monomers applied as medical adhesives. Another advantage of the process proposed is the fact that it does not require the use of non-recyclable, high-boiling point solvents (such as tricresyl phosphate) and/or dangerous, corrosive gases (SO2) which required special safety and purification procedures.
[12] According to the process of the present invention, the poly(alkyl- a -cyanoacrylate) or poly(alkoxyalkyl- a -cyanoacrylate) condensation product is mixed with a depoly-merisation system comprising phosphorous pentoxide (P205), hydroquinone, ortho -phosphoric acid (crystalline or liquid) and para-toluenesulfonic acid in a one condenser batch reactor, heated within the range of 100-300 C, preferably 150-and more preferably 180-220('C, and operating under a vacuum within the limits of 50-0.5 Torr (7x 10-3 - 7x 10-5 MPa), preferably 20-1 Torr (3x 10-3 - 1.3x 10-4 MPa) and more preferably 10-5 Torr (1.3x 10-3 - 7x 10-4 MPa), both depending on the structure of the monomer to be prepared.
[13] Also depending on the structure of the monomer to be prepared, the relation between the phosphorous pentoxide and the hydroquinone is in the range, wt.
parts, from 1:10 to 10:1, preferably between 1:1 and 1:5, more preferably between 1:1 and 1:3, and the relation between the ortho-phosphoric acid and para-toluenesulfonic acid is in the range from, wt. parts, 20:1 and 1:20, preferably between 15:1 and 10:1.
parts, from 1:10 to 10:1, preferably between 1:1 and 1:5, more preferably between 1:1 and 1:3, and the relation between the ortho-phosphoric acid and para-toluenesulfonic acid is in the range from, wt. parts, 20:1 and 1:20, preferably between 15:1 and 10:1.
[14] The present invention will now be described more specifically with reference to some typical examples. It is to be noted that the following examples are presented herein for the purpose of illustration and description and are not intended to be exhaustive or to limit the invention to the precise form of the present description.
Example 1 [15] 160 parts (1.4 mol) of ethyl cyanoacetate, 170 parts of toluene, 20 parts of paraformaldehyde and 0.5 parts of piperidine were mixed and heated in a 0.51itre , stirred reaction flask, fitted with a thermometer, condenser and a Dean-Stark trap. The mixture was refluxed while stirring until removing the theoretical amount of con-densation water. Thereafter, the reaction vessel containing toluene solution of poly(ethyl-a-cyanoacrylate) was cooled down to room temperature. 4 parts of fresh phosphorus pentoxide and 1.5 parts of hydroquinone (weight ratio of 2.67:1.00), as well as 1 part of para-toluenesulfonic acid and 10 parts of ortho-phosphoric acid (weight ratio of 1:10) were then added with good stirring. The toluene solvent was removed under reduced pressure and the residue depolymerised by heating up to under a vacuum of 15 Torr. The distillate (102 parts) was collected in a cold flask containing 0.1 part sulphuric acid and 0.05 part of hydroquinone and subjected to additional vacuum distillation to get 94 parts of high-purity (+99%, GC) ethyl-a-cyanoacrylate.
Exainple 2 [16] Example 1 is repeated except that 120 parts of butyl cyanoacetate were mixed with 23 parts of paraformaldehyde, 0.5 parts of piperidine in 150 parts of toluene using the same reaction vessel and conditions. Depolymerisation at 190 C under a vacuum of 10 Torr was performed in the presence of 3 parts of P205, 2 parts of hydroquinone (weight ratio 1.5:1.0), 1 part of para-toluenesulfonic acid and 10 parts of ortho-phosphoric acid (weight ratio 1:10). After purification by additional vacuum distillation, 65 parts of high-purity (+99%, GC) and stabilized butyl-a-cyanoacrylate were obtained.
Exainple 3 [17] Example 1 is repeated except that 180 parts of 2-ethoxyethyl cyanoacetate were mixed with 32 parts of paraformaldehyde, 0.8 parts of piperidine in 200 parts of toluene using the same reaction vessel and conditions. The resulting poly(ethoxyethyl-a-cyanoacrylate) was depolymerised at 210 C under a vacuum of 5.0 Torr in the presence of 6 parts of P205, 3 parts of hydroquinone (weight ratio of 2:1), 0.5 parts of para-toluenesulfonic acid and 5 parts of ortho-phosphoric acid (weight ratio of 1:10). After purification by additional vacuum distillation, 62 parts of high-purity (+98%, GC) and stabilized 2-ethoxyethyl-a-cyanoacrylate were obtained.
Example 1 [15] 160 parts (1.4 mol) of ethyl cyanoacetate, 170 parts of toluene, 20 parts of paraformaldehyde and 0.5 parts of piperidine were mixed and heated in a 0.51itre , stirred reaction flask, fitted with a thermometer, condenser and a Dean-Stark trap. The mixture was refluxed while stirring until removing the theoretical amount of con-densation water. Thereafter, the reaction vessel containing toluene solution of poly(ethyl-a-cyanoacrylate) was cooled down to room temperature. 4 parts of fresh phosphorus pentoxide and 1.5 parts of hydroquinone (weight ratio of 2.67:1.00), as well as 1 part of para-toluenesulfonic acid and 10 parts of ortho-phosphoric acid (weight ratio of 1:10) were then added with good stirring. The toluene solvent was removed under reduced pressure and the residue depolymerised by heating up to under a vacuum of 15 Torr. The distillate (102 parts) was collected in a cold flask containing 0.1 part sulphuric acid and 0.05 part of hydroquinone and subjected to additional vacuum distillation to get 94 parts of high-purity (+99%, GC) ethyl-a-cyanoacrylate.
Exainple 2 [16] Example 1 is repeated except that 120 parts of butyl cyanoacetate were mixed with 23 parts of paraformaldehyde, 0.5 parts of piperidine in 150 parts of toluene using the same reaction vessel and conditions. Depolymerisation at 190 C under a vacuum of 10 Torr was performed in the presence of 3 parts of P205, 2 parts of hydroquinone (weight ratio 1.5:1.0), 1 part of para-toluenesulfonic acid and 10 parts of ortho-phosphoric acid (weight ratio 1:10). After purification by additional vacuum distillation, 65 parts of high-purity (+99%, GC) and stabilized butyl-a-cyanoacrylate were obtained.
Exainple 3 [17] Example 1 is repeated except that 180 parts of 2-ethoxyethyl cyanoacetate were mixed with 32 parts of paraformaldehyde, 0.8 parts of piperidine in 200 parts of toluene using the same reaction vessel and conditions. The resulting poly(ethoxyethyl-a-cyanoacrylate) was depolymerised at 210 C under a vacuum of 5.0 Torr in the presence of 6 parts of P205, 3 parts of hydroquinone (weight ratio of 2:1), 0.5 parts of para-toluenesulfonic acid and 5 parts of ortho-phosphoric acid (weight ratio of 1:10). After purification by additional vacuum distillation, 62 parts of high-purity (+98%, GC) and stabilized 2-ethoxyethyl-a-cyanoacrylate were obtained.
[18] The foregoing examples of the preferred embodiments of this invention are presented for purposes of illustration and description. Various modifications or variations are possible. The embodiments were chosen and described to provide the best illustration of the principles of this invention and its practical application to thereby enable those skilled in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the present invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.
References Cited [19]
= Alan E. Ardis, to Goodrich B. F. Co., NY: 'Preparation of monomeric alkyl-a-cyanoacrylates', US patent 2,467,927 (April 19, 1949 ).
= Frederick B. Joyner and Gary F. Hawkins, to Eastman Kodak Co, NY:
'Method of making of a-cyanoacrylates', US patent 2,721,858 ( October 25, 1955).
= Frederick B. Joyner and Newton H. Shearer Jun., to Eastman Kodak Co., NY:
'Preparation of monomeric a-cyanoacrylates', US patent 2,756,251 (July 24, 1956).
= Robert Rabinowitz, to American Cyanamid Co, Maine :'Preparation of alkyl-and aryl-a-cyanoacrylates', US patent 3,444,233 (May 13, 1969 ).
= Tien-Lu Wang, Tso-Chi Chiu, Kun-Chuo Chen, to Industrial Technology Research Institute, Chutung , Taiwan : 'Method for making of alkyl-a-cyanoacrylates from polyalkyl-a-cyanoacrylates', US patent No 5,436,363, (July 25, 1995).
= Neil Hunter Ray and Peter Doran, to ICI Ltd., UK :'Preparation of a-cyanoacrylic esters', US patent 3,463,804 (August 26, 1969 ).
= Carl J. Buck, to Johnson & Johnson, NY,'Modified cyanoacrylate monomers and methods for preparation', US patent 4,012,402 (March 15, 1977).
= Y. B. Vojtekunas, A. M. Polyakova, K. A. Mager, Y. B. Kohanov, A. I.
Vojtkov, to Institute of Organometallic compounds, USSR Academy of Sciences, USSR, 'Method of making esters of the a-cyanoacrylic acid', USSR
authorship certification 726,086 (March 1980) (In Russian).
= Kaspar Schulter and Klaus Marten, to Henkel KGaA, BRD, 'a-Cyanacrylsaure', Offenlegungsschrift DE 3415181 Al (October 31, 1985 ) (in German).
= Alan E. Ardis, to Goodrich B. F. Co., NY: 'Preparation of monomeric alkyl-a-cyanoacrylates', US patent 2,467,926 (April 19, 1949 ).
= John B. Long, to Wingfoot Co., Delaware,'Derivatives of fatty acids and method of preparing same', US patent 2,391,251 ( December 18, 1945 ).
References Cited [19]
= Alan E. Ardis, to Goodrich B. F. Co., NY: 'Preparation of monomeric alkyl-a-cyanoacrylates', US patent 2,467,927 (April 19, 1949 ).
= Frederick B. Joyner and Gary F. Hawkins, to Eastman Kodak Co, NY:
'Method of making of a-cyanoacrylates', US patent 2,721,858 ( October 25, 1955).
= Frederick B. Joyner and Newton H. Shearer Jun., to Eastman Kodak Co., NY:
'Preparation of monomeric a-cyanoacrylates', US patent 2,756,251 (July 24, 1956).
= Robert Rabinowitz, to American Cyanamid Co, Maine :'Preparation of alkyl-and aryl-a-cyanoacrylates', US patent 3,444,233 (May 13, 1969 ).
= Tien-Lu Wang, Tso-Chi Chiu, Kun-Chuo Chen, to Industrial Technology Research Institute, Chutung , Taiwan : 'Method for making of alkyl-a-cyanoacrylates from polyalkyl-a-cyanoacrylates', US patent No 5,436,363, (July 25, 1995).
= Neil Hunter Ray and Peter Doran, to ICI Ltd., UK :'Preparation of a-cyanoacrylic esters', US patent 3,463,804 (August 26, 1969 ).
= Carl J. Buck, to Johnson & Johnson, NY,'Modified cyanoacrylate monomers and methods for preparation', US patent 4,012,402 (March 15, 1977).
= Y. B. Vojtekunas, A. M. Polyakova, K. A. Mager, Y. B. Kohanov, A. I.
Vojtkov, to Institute of Organometallic compounds, USSR Academy of Sciences, USSR, 'Method of making esters of the a-cyanoacrylic acid', USSR
authorship certification 726,086 (March 1980) (In Russian).
= Kaspar Schulter and Klaus Marten, to Henkel KGaA, BRD, 'a-Cyanacrylsaure', Offenlegungsschrift DE 3415181 Al (October 31, 1985 ) (in German).
= Alan E. Ardis, to Goodrich B. F. Co., NY: 'Preparation of monomeric alkyl-a-cyanoacrylates', US patent 2,467,926 (April 19, 1949 ).
= John B. Long, to Wingfoot Co., Delaware,'Derivatives of fatty acids and method of preparing same', US patent 2,391,251 ( December 18, 1945 ).
Claims
Claims The process for the preparation of alkyl or alcoxyalkyl-a-cyanoacrylates of general formula (1) wherein R is a C1-C10-alkyl or alkoxyalkyl residue characterized by comprising the depolymerisation of the corresponding poly(alkyl-.alpha.-cyanoacrylate) or poly(alkoxyalkyl-.alpha.-cyanoacrylate)in the presence of a multi-component stabilizing system, which comprises (a) phosphorus pentoxide;
(b) bydroquinone;
(c) ortho-phosphoric acid; and (d) para-toluenesulfonic acid.
A process according to claim 1, characterized by the relation between the phosphorous pentoxide and the hydroquinone being in the range, wt. parts, from 1:10 to 10:1, preferably between 1:1 and 1:5, more preferably between 1:1 and 1:3.
A process according to claim 1, characterized by the relation between the ortho-phosphoric acid and the para-toluenesulfonic acid being in the range from, wt. parts, 20:1 and 1:20, preferably between 15:1 and 10:1.
A process according to claim 1, characterized by said alkyl-.alpha.-cyanoacrylate being ethyl-.alpha.-cyanoacrylate and said poly(alkyl-.alpha.-cyanoacrylate) being poly(ethyl-.alpha.-cyanoacrylate).
A process according to claim 1, characterized by said alkyl-.alpha.-cyanoacrylate being butyl-.alpha.-cyanoacrylate, and said poly(butyl-.alpha.-cyanoacrylate) being poly(ethyl-.alpha.-cyanoacrylate).
A process according to claims 1, characterized by said alkoxyalkyl-a-cyanoacrylate being 2-ethoxyethyl-.alpha.-cyanoacrylate, and said poly(alkoxyalkyl-.alpha.-cyanoacrylate) being poly(2-ethoxyethyl-.alpha.-cyanoacrylate).
A process according to claim 1, characterized by the depolymerisation step being performed in the range of temperatures between 100 and 300°C, preferably between 150 and 250°C and more preferably between 180 and 220°C.
A process according to claim 1, characterized by the depolymerisation step being carried out in vacuum in the range from 50 to 0.5 Torr, preferably between 20 and 1 Torr and more preferably between 10 and 5 Torr.
The process according to any of the preceding claims characterized by further comprising an additional step of vacuum distillation.
Use of the process, according to any of the preceding claims, characterized for being applied to the preparation of alkyl or alcoxyalkyl-.alpha.-cyanoacrylates of general formula (1).
Use of the process, according to claim 10, characterized for being applied to the preparation of technical or medical adhesives based on the alkyl or alcoxyalkyl-.alpha.-cyanoacrylates of general formula (I).
(b) bydroquinone;
(c) ortho-phosphoric acid; and (d) para-toluenesulfonic acid.
A process according to claim 1, characterized by the relation between the phosphorous pentoxide and the hydroquinone being in the range, wt. parts, from 1:10 to 10:1, preferably between 1:1 and 1:5, more preferably between 1:1 and 1:3.
A process according to claim 1, characterized by the relation between the ortho-phosphoric acid and the para-toluenesulfonic acid being in the range from, wt. parts, 20:1 and 1:20, preferably between 15:1 and 10:1.
A process according to claim 1, characterized by said alkyl-.alpha.-cyanoacrylate being ethyl-.alpha.-cyanoacrylate and said poly(alkyl-.alpha.-cyanoacrylate) being poly(ethyl-.alpha.-cyanoacrylate).
A process according to claim 1, characterized by said alkyl-.alpha.-cyanoacrylate being butyl-.alpha.-cyanoacrylate, and said poly(butyl-.alpha.-cyanoacrylate) being poly(ethyl-.alpha.-cyanoacrylate).
A process according to claims 1, characterized by said alkoxyalkyl-a-cyanoacrylate being 2-ethoxyethyl-.alpha.-cyanoacrylate, and said poly(alkoxyalkyl-.alpha.-cyanoacrylate) being poly(2-ethoxyethyl-.alpha.-cyanoacrylate).
A process according to claim 1, characterized by the depolymerisation step being performed in the range of temperatures between 100 and 300°C, preferably between 150 and 250°C and more preferably between 180 and 220°C.
A process according to claim 1, characterized by the depolymerisation step being carried out in vacuum in the range from 50 to 0.5 Torr, preferably between 20 and 1 Torr and more preferably between 10 and 5 Torr.
The process according to any of the preceding claims characterized by further comprising an additional step of vacuum distillation.
Use of the process, according to any of the preceding claims, characterized for being applied to the preparation of alkyl or alcoxyalkyl-.alpha.-cyanoacrylates of general formula (1).
Use of the process, according to claim 10, characterized for being applied to the preparation of technical or medical adhesives based on the alkyl or alcoxyalkyl-.alpha.-cyanoacrylates of general formula (I).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PT103272 | 2005-05-06 | ||
| PT103272A PT103272A (en) | 2005-05-06 | 2005-05-06 | PROCESS FOR THE PREPARATION OF ALKYLOXYCYCLATHS OF ALKYL AND ALCOXYALKYL BY POLYPOOLIZATION OF POLY (ALPHA-CIANOACRYLATES OF ALKYL OR ALCOXYLOCYL |
| PCT/IB2006/051426 WO2006120628A2 (en) | 2005-05-06 | 2006-05-05 | PROCESS FOR PREPARATION OF ALKYL AND ALCOXYALKYL-α-CYANOACRYLATES BY DEPOLYMERISATION OF POLY(ALKYL-α CYANOACRYLATES) OR POLY(ALCOXYALKYL-α-CYANOACRYLATES) AND ITS USAGE AS TECHNICAL AND/OR MEDICAL ADHESIVE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2608183A1 true CA2608183A1 (en) | 2006-11-16 |
Family
ID=36945317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002608183A Abandoned CA2608183A1 (en) | 2005-05-06 | 2006-05-05 | Process for preparation of alkyl and alcoxyalkyl-.alpha.-cyanoacrylates by depolymerisation of poly(alkyl-.alpha.-cyanoacrylates) or poly(alcoxyalkyl-.alpha.-cranoacrylates) and its usage as technical and/or medical adhesive |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20090018360A1 (en) |
| EP (1) | EP1885690B1 (en) |
| AT (1) | ATE483680T1 (en) |
| CA (1) | CA2608183A1 (en) |
| DE (1) | DE602006017357D1 (en) |
| PT (2) | PT103272A (en) |
| WO (1) | WO2006120628A2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070213553A1 (en) * | 2006-03-10 | 2007-09-13 | Hongbo Liu | Method for producing a cyanoacrylate monomer |
| GB2443411B (en) * | 2006-11-02 | 2011-12-21 | Chemence Ltd | Process for producing a monomer |
| CN109678758B (en) * | 2019-01-31 | 2021-11-16 | 河北诚信集团有限公司 | Synthetic method of alpha-cyanoacrylate |
| CN109796370B (en) * | 2019-01-31 | 2021-08-31 | 河北诚信集团有限公司 | Recovery method of alpha-cyanoacrylate dry glue |
| CN113173867B (en) * | 2021-03-26 | 2023-05-30 | 湖南浩森胶业有限公司 | Preparation method of ethyl cyanoacrylate |
| EP4209484A1 (en) * | 2022-07-11 | 2023-07-12 | Aleardis Ltd. | Process for preparing electron-deficient olefin monomers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3254111A (en) * | 1960-12-09 | 1966-05-31 | Eastman Kodak Co | Esters of alpha-cyanoacrylic acid and process for the manufacture thereof |
| DE19921484A1 (en) * | 1999-05-08 | 2000-11-16 | Degussa | Cyanoacrylate preparation involves condensation of cyanoacetic esters with formaldehyde followed by depolymerization, with polyethylene glycol dialkyl ether present in both stages |
-
2005
- 2005-05-06 PT PT103272A patent/PT103272A/en not_active Application Discontinuation
-
2006
- 2006-05-05 AT AT06744875T patent/ATE483680T1/en not_active IP Right Cessation
- 2006-05-05 EP EP06744875A patent/EP1885690B1/en active Active
- 2006-05-05 DE DE602006017357T patent/DE602006017357D1/en active Active
- 2006-05-05 PT PT06744875T patent/PT1885690E/en unknown
- 2006-05-05 CA CA002608183A patent/CA2608183A1/en not_active Abandoned
- 2006-05-05 US US11/913,754 patent/US20090018360A1/en not_active Abandoned
- 2006-05-05 WO PCT/IB2006/051426 patent/WO2006120628A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| US20090018360A1 (en) | 2009-01-15 |
| EP1885690A2 (en) | 2008-02-13 |
| ATE483680T1 (en) | 2010-10-15 |
| WO2006120628A3 (en) | 2006-12-21 |
| WO2006120628B1 (en) | 2007-03-22 |
| PT103272A (en) | 2006-11-30 |
| EP1885690B1 (en) | 2010-10-06 |
| DE602006017357D1 (en) | 2010-11-18 |
| WO2006120628A2 (en) | 2006-11-16 |
| PT1885690E (en) | 2011-01-13 |
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